A New Approach to Micropatterning: Application of Potential-Assisted Ion Transfer at the Liquid−Liquid Interface for the Local Metal Deposition

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Abstract
A new approach to micropatterning is demonstrated. The approach is based on driving an electrochemical process at the solid−liquid interface through the formation of a flux of ions from a micropipet that is held in close proximity to the surface. The flux of ions is generated by the so-called potential assisted ion transfer at the interface between two immiscible electrolyte solutions (ITIES). As a model system, the local deposition of silver was examined. Specifically, a constant potential, which was applied to a micropipet filled with an aqueous solution of silver ions, caused the transfer of Ag+ into the outer nitrobenzene (NB) solution that consisted of an electrolyte, tetrabutylammonium tetrakis[4-chlorophenyl]borate (TBATPBCl). To facilitate the transfer of silver ions a macrocyclic ligand, that is, dibenzo-24-crown-8 (DB24C8), was added to the organic phase. The Faradaic current of this micro-ITIES was used as a means of controlling the tip−surface distance in scanning electrochemical microscopy (SECM) and depositing silver microstructures on a gold substrate.